We have successfully synthesized ultrathin nanowires of pure Pt, Pt99Ni1, Pt9Ni1, and Pt7Ni3using a modified room‐temperature soft‐template method. Analysis of both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) results found that the Pt7Ni3samples yielded the best performance with specific activities of 0.36 and 0.34 mA/cm2respectively. Additionally, formic acid oxidation reaction (FAOR) tests noted that both Pt and PtNi nanowires oxidize small organic molecules (SOMs) via an indirect pathway. CO oxidation data suggests little measurable performance without any pre‐reduction treatment; however, after annealing in H2, we detected significantly improved CO2formation for both Pt9Ni1and Pt7Ni3motifs. These observations highlight the importance of pre‐treating these nanowires under a reducing atmosphere to enhance their performance for CO oxidation. To explain these findings, we collected extended x‐ray adsorption fine structure (EXAFS) spectroscopy data, consistent with the presence of partial alloying with a tendency for Pt and Ni to segregate, thereby implying the formation of a Pt‐rich shell coupled with a Ni‐rich core. We also observed that the degree of alloying within the nanowires increased after annealing in a reducing atmosphere, a finding deduced through analysis of the coordination numbers and calculations of Cowley's short range order parameters.
Reconciling structure prediction of alloyed, ultrathin nanowires with spectroscopy
A number of complementary, synergistic advances are reported herein. First, we describe the ‘first-time’ synthesis of ultrathin Ru 2 Co 1 nanowires (NWs) possessing average diameters of 2.3 ± 0.5 nm using a modified surfactant-mediated protocol. Second, we utilize a combination of quantitative EDS, EDS mapping (along with accompanying line-scan profiles), and EXAFS spectroscopy results to probe the local atomic structure of not only novel Ru 2 Co 1 NWs but also ‘control’ samples of analogous ultrathin Ru 1 Pt 1 , Au 1 Ag 1 , Pd 1 Pt 1 , and Pd 1 Pt 9 NWs. We demonstrate that ultrathin NWs possess an atomic-level geometry that is fundamentally dependent upon their intrinsic chemical composition. In the case of the PdPt NW series, EDS mapping data are consistent with the formation of a homogeneous alloy, a finding further corroborated by EXAFS analysis. By contrast, EXAFS analysis results for both Ru 1 Pt 1 and Ru 2 Co 1 imply the generation of homophilic structures in which there is a strong tendency for the clustering of ‘like’ atoms; associated EDS results for Ru 1 Pt 1 convey the same conclusion, namely the production of a heterogeneous structure. Conversely, EDS mapping data for Ru 2 Co 1 suggests a uniform distribution of both elements. In the singular case of Au 1 Ag 1 , EDS mapping results are suggestive of a homogeneous alloy, whereas EXAFS analysis pointed to Ag segregation at the surface and an Au-rich core, within the context of a core–shell structure. These cumulative outcomes indicate that only a combined consideration of both EDS and EXAFS results can provide for an accurate representation of the local atomic structure of ultrathin NW motifs.
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- Award ID(s):
- 1807640
- NSF-PAR ID:
- 10223801
- Date Published:
- Journal Name:
- Chemical Science
- ISSN:
- 2041-6520
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Transparent microelectrodes have received much attention from the biomedical community due to their unique advantages in concurrent crosstalk‐free electrical and optical interrogation of cell/tissue activity. Despite recent progress in constructing transparent microelectrodes, a major challenge is to simultaneously achieve desirable mechanical stretchability, optical transparency, electrochemical performance, and chemical stability for high‐fidelity, conformal, and stable interfacing with soft tissue/organ systems. To address this challenge, we have designed microelectrode arrays (MEAs) with gold‐coated silver nanowires (Au–Ag NWs) by combining technical advances in materials, fabrication, and mechanics. The Au coating improves both the chemical stability and electrochemical impedance of the Au–Ag NW microelectrodes with only slight changes in optical properties. The MEAs exhibit a high optical transparency >80% at 550 nm, a low normalized 1 kHz electrochemical impedance of 1.2–7.5 Ω cm2, stable chemical and electromechanical performance after exposure to oxygen plasma for 5 min, and cyclic stretching for 600 cycles at 20% strain, superior to other transparent microelectrode alternatives. The MEAs easily conform to curvilinear heart surfaces for colocalized electrophysiological and optical mapping of cardiac function. This work demonstrates that stretchable transparent metal nanowire MEAs are promising candidates for diverse biomedical science and engineering applications, particularly under mechanically dynamic conditions.
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In the context of developing novel fuel cell catalysts, we have successfully synthesized in high yields not only ultrathin nanowires with compositions of Pt1Ru1 and Pt3Ru1 but also more complex spoke-like dendritic clusters of Pt1Ru1 and Pt1Ru9 in ambient pressure under relatively straightforward, solution-based reaction conditions, mediated by either CTAB (cetyltrimethylammonium bromide) or oleylamine (OAm), respectively. EXAFS analysis allowed us to determine the homogeneity of as-prepared samples. Based on this analysis, only the Pt3Ru1 sample was found to be relatively homogeneous. All of the other samples yielded results, suggestive of a tendency for the elements to segregate into clusters of ‘like’ atoms. We have also collected complementary HRTEM EDS mapping data, which support the idea of a segregation of elements consistent with the EXAFS results. We attribute the differences in the observed morphologies and elemental distributions within as-prepared samples to the presence of varying surfactants and heating environments, employed in these reactions. Methanol oxidation reaction (MOR) measurements indicated a correlation of specific activity (SA) values not only with intrinsic chemical composition and degree of alloying but also with the reaction process used to generate the nanoscale motifs in the first place. Specifically, the observed performance of samples tested decreased as a function of chemical composition (surfactant used in their synthesis), as follows: Pt3Ru1 (CTAB) > Pt1Ru1 (CTAB) > Pt1Ru1 (OAm) > Pt1Ru9 (OAm).more » « less
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Conducting probe atomic force microscopy (CP-AFM) was employed to examine electron tunneling in self-assembled monolayer (SAM) junctions. A 2.3 nm long perylene tetracarboxylic acid diimide (PDI) acceptor molecule equipped with isocyanide linker groups was synthesized, adsorbed onto Ag, Au and Pt substrates, and the current–voltage ( I – V ) properties were measured by CP-AFM. The dependence of the low-bias resistance ( R ) on contact work function indicates that transport is LUMO-assisted (‘n-type behavior’). A single-level tunneling model combined with transition voltage spectroscopy (TVS) was employed to analyze the experimental I – V curves and to extract the effective LUMO position ε l = E LUMO − E F and the effective electronic coupling ( Γ ) between the PDI redox core and the contacts. This analysis revealed a strong Fermi level ( E F ) pinning effect in all the junctions, likely due to interface dipoles that significantly increased with increasing contact work function, as revealed by scanning Kelvin probe microscopy (SKPM). Furthermore, the temperature ( T ) dependence of R was found to be substantial. For Pt/Pt junctions, R varied more than two orders of magnitude in the range 248 K < T < 338 K. Importantly, the R ( T ) data are consistent with a single step electron tunneling mechanism and allow independent determination of ε l , giving values compatible with estimates of ε l based on analysis of the full I – V data. Theoretical analysis revealed a general criterion to unambiguously rule out a two-step transport mechanism: namely, if measured resistance data exhibit a pronounced Arrhenius-type temperature dependence, a two-step electron transfer scenario should be excluded in cases where the activation energy depends on contact metallurgy. Overall, our results indicate (1) the generality of the Fermi level pinning phenomenon in molecular junctions, (2) the utility of employing the single level tunneling model for determining essential electronic structure parameters ( ε l and Γ ), and (3) the importance of changing the nature of the contacts to verify transport mechanisms.more » « less
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Metal phosphides are promising catalysts for hydrocarbon transformations, but computational screening is complicated by their diverse structures and compositions. To disentangle structural from compositional contributions, here we explore the metal-rich M 2 P (M = Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Pt) series in hexagonal and orthorhombic structures that are common to a subset of these materials, using supercell density functional theory (DFT). To understand the contribution of metal choice to utility for catalytic ethane dehydrogenation (EDH), we compute and compare the adsorption of key EDH intermediates across low-index surface terminations. These materials expose both metal and phosphide sites. Calculations show that binding energies at metal sites correlate with the bulk metals, with P incorporation either enhancing or suppressing binding. Phosphide sites compete with metal sites for adsorbates and tend to suppress overactivation by destabilizing highly dehydrogenated species engaging in C–H bond breaking. Results are generally insensitive to bulk structure and surface facet. Results suggest metal-rich Pd phosphides to have favorable adsorption characteristics for catalytic dehydrogenation, consistent with recent observations.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1sc00627d
